Method of manufacturing semiconductor device, substrate processing apparatus, recording medium and method of processing substrate

ABSTRACT

There is included (a) forming a film on a substrate by supplying a first processing gas to the substrate in a process container; (b) forming a first pre-coated film, which has a first thickness and has a material different from a material of the film formed in (a), in the process container by supplying a second processing gas into the process container in a state in which the substrate does not exist in the process container; and (c) forming a second pre-coated film, which has a second thickness smaller than the first thickness and has the same material as the material of the film formed in (a), on the first pre-coated film formed in the process container by supplying a third processing gas into the process container in the state in which the substrate does not exist in the process container.

CROSS-REFERENCE TO RELATED APPLICATION

This application is based upon and claims the benefit of priority fromJapanese Patent Application No. 2019-145220, filed on Aug. 7, 2019, theentire contents of which are incorporated herein by reference.

TECHNICAL FIELD

The present disclosure relates to a method of manufacturing asemiconductor device, a substrate processing apparatus, and a recordingmedium.

BACKGROUND

In a related art, as an example of processes of manufacturing asemiconductor device, a process of processing a substrate in a processcontainer of a substrate processing apparatus is often carried out.

SUMMARY

The present disclosure provides some embodiments of a technique capableof improving a productivity by shortening a downtime of a substrateprocessing apparatus.

According to one or more embodiments of the present disclosure, there isprovided a technique that includes (a) forming a film on a substrate bysupplying a first processing gas to the substrate in a processcontainer; (b) forming a first pre-coated film, which has a firstthickness and has a material different from a material of the filmformed in (a), in the process container by supplying a second processinggas into the process container in a state in which the substrate doesnot exist in the process container; and (c) forming a second pre-coatedfilm, which has a second thickness smaller than the first thickness andhas the same material as the material of the film formed in (a), on thefirst pre-coated film formed in the process container by supplying athird processing gas into the process container in the state in whichthe substrate does not exist in the process container.

BRIEF DESCRIPTION OF DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of the specification, illustrate embodiments of the presentdisclosure.

FIG. 1 is a schematic configuration view of a vertical type processfurnace of a substrate processing apparatus suitably used in one or moreembodiments of the present disclosure, in which a portion of the processfurnace is shown in a vertical cross sectional view.

FIG. 2 is a schematic configuration view of a vertical type processfurnace of the substrate processing apparatus suitably used in one ormore embodiments of the present disclosure, in which a portion of theprocess furnace is shown in a cross sectional view taken along line A-Ain FIG. 1.

FIG. 3 is a schematic configuration view of a controller of thesubstrate processing apparatus suitably used in one or more embodimentsof the present disclosure, in which a control system of the controlleris shown in a block diagram.

FIG. 4 is a view illustrating a substrate processing sequence accordingto one or more embodiments of the present disclosure.

FIG. 5 is a view illustrating a gas supply sequence in film formationaccording to one or more embodiments of the present disclosure.

FIG. 6A is a schematic cross sectional view illustrating an inner wallof a reaction tube after pre-coating according to a comparative example,and FIG. 6B is a schematic sectional view illustrating an inner wall ofa reaction tube after pre-coating according to this example.

FIG. 7 is a view illustrating a comparison between a pre-coating timewhen a pre-coated film according to a comparative example is formed anda pre-coating time when a pre-coated film according to this example isformed.

FIG. 8A is a view illustrating a thickness of a film formed on asubstrate arranged in each of top (TOP), center (CEN), and bottom (BTM)by first film formation after pre-coating by comparison between thecomparative example and this example, FIG. 8B is a view illustrating awafer in-plane film thickness uniformity of the film formed on thesubstrate arranged in each of TOP, CEN, and BTM by the first filmformation after pre-coating by comparison between the comparativeexample and this example, FIG. 8C is a view illustrating a number ofparticles adhered to the film formed on the substrate arranged in eachof TOP, CEN, and BTM by the first film formation after pre-coating bycomparison between the comparative example and this example, FIG. 8D isa view illustrating a refractive index of the film formed on thesubstrate arranged in each of TOP, CEN, and BTM by the first filmformation after pre-coating by comparison between the comparativeexample and this example, FIG. 8E is a view illustrating a compositionratio of the film formed on the substrate by the first film formationafter pre-coating by comparison between the comparative example and thisexample, and FIG. 8F is a view illustrating a wet etching rate of thefilm formed on the substrate by the first film formation afterpre-coating by comparison between the comparative example and thisexample.

DETAILED DESCRIPTION

Reference will now be made in detail to various embodiments, examples ofwhich are illustrated in the accompanying drawings. In the followingdetailed description, numerous specific details are set forth in orderto provide a thorough understanding of the present disclosure. However,it will be apparent to one of ordinary skill in the art that the presentdisclosure may be practiced without these specific details. In otherinstances, well-known methods, procedures, systems, and components havenot been described in detail so as not to unnecessarily obscure aspectsof the various embodiments.

One or More Embodiments of the Present Disclosure

One or more embodiments of the present disclosure will now be describedmainly with reference to FIGS. 1 to 5.

(1) Configuration of the Substrate Processing Apparatus

As illustrated in FIG. 1, a process furnace 202 includes a heater 207 asa heating mechanism (temperature regulator). The heater 207 has acylindrical shape and is supported by a holding plate so as to bevertically installed. The heater 207 functions as an activationmechanism (an excitation part) configured to thermally activate (excite)a gas.

A reaction tube 203 is disposed inside the heater 207 to be concentricwith the heater 207. The reaction tube 203 is made of a heat resistantmaterial, e.g., quartz (SiO₂), silicon carbide (SiC), or the like, andhas a cylindrical shape with its upper end closed and its lower endopened. A manifold 209 is disposed below the reaction tube 203 in aconcentric relationship with the reaction tube 203. The manifold 209 ismade of a metal material, e.g., stainless steel (SUS), and has acylindrical shape with its upper and lower ends opened. The upper end ofthe manifold 209 engages with the lower end of the reaction tube 203.The manifold 209 is configured to support the reaction tube 203. AnO-ring 220 a as a seal member is installed between the manifold 209 andthe reaction tube 203. Similar to the heater 207, the reaction tube 203is vertically installed. A processing container (reaction container)mainly includes the reaction tube 203 and the manifold 209. A processchamber 201 is formed in a hollow cylindrical portion of the processingcontainer. The process chamber 201 is configured to accommodate wafers200 as substrates. The process to the wafers 200 is performed in theprocess chamber 201.

Nozzles 249 a and 249 b as first and second suppliers are installed inthe process chamber 201 so as to penetrate a sidewall of the manifold209. The nozzles 249 a and 249 b will be referred to as a first nozzleand a second nozzle, respectively. The nozzles 249 a and 249 b are eachmade of a heat resistant material which is a non-metallic material suchas quartz, SiC or the like. The nozzles 249 a and 249 b are configuredas common nozzles used for supplying plural kinds of gases,respectively.

Gas supply pipes 232 a and 232 b as first and second pipes are connectedto the nozzles 249 a and 249 b, respectively. The gas supply pipes 232 aand 232 b are configured as common pipes used for supplying plural kindsof gases, respectively. MFCs (Mass flow controllers) 241 a and 241 b,which are flow rate controllers (flow rate control parts), and valves243 a and 243 b, which are opening/closing valves, are installed in thegas supply pipes 232 a and 232 b sequentially from the correspondingupstream sides of gas flow, respectively. Gas supply pipes 232 c, 232 e,and 232 h are respectively connected to the gas supply pipe 232 a at thedownstream side of the valve 243 a. MFCs 241 c, 241 e, and 241 h andvalves 243 c, 243 e, and 243 h are installed in the gas supply pipes 232c, 232 e, and 232 h sequentially from the corresponding upstream sidesof gas flow, respectively. Gas supply pipes 232 d, 232 f, 232 g, and 232i are respectively connected to the gas supply pipe 232 b at thedownstream side of the valve 243 b. MFCs 241 d, 241 f, 241 g, and 241 iand valves 243 d, 243 f, 243 g, and 243 i are installed in the gassupply pipes 232 d, 232 f, 232 g, and 232 i sequentially from thecorresponding upstream sides of gas flow, respectively.

The gas supply pipes 232 a to 232 i are each made of a metal materialcontaining iron (Fe) and nickel (Ni). The material of the gas supplypipes 232 a to 232 i may contain Fe, Ni, and chromium (Cr), or maycontain Fe, Ni, Cr, and molybdenum (Mo). That is, as the material of thegas supply pipes 232 a to 232 i, it may be possible to suitably use, inaddition to SUS, for example, Hastelloy (registered trademark) withenhanced heat resistance and corrosion resistance by adding Fe, Mo, Cr,or the like to Ni, Inconel (registered trademark) with enhanced heatresistance and corrosion resistance by adding Fe, Cr, niobium (Nb), Mo,or the like to Ni, or the like. Furthermore, the material of themanifold 209 described above and materials of a seal cap 219, a rotaryshaft 255, and an exhaust pipe 231 as described hereinbelow may besimilar to those of the gas supply pipes 232 a to 232 i.

As illustrated in FIG. 2, the nozzles 249 a and 249 b are disposed in aspace with an annular plan-view shape between the inner wall of thereaction tube 203 and the wafers 200 such that the nozzles 249 a and 249b extend upward along an arrangement direction of the wafers 200 from alower portion of the inner wall of the reaction tube 203 to an upperportion of the inner wall of the reaction tube 203. Specifically, thenozzles 249 a and 249 b are installed at a lateral side of a waferarrangement region in which the wafers 200 are arranged, namely in aregion which horizontally surrounds the wafer arrangement region, so asto extend along the wafer arrangement region. Gas supply holes 250 a and250 b for supplying a gas are installed at the side surfaces of thenozzles 249 a and 249 b, respectively. The gas supply holes 250 a and250 b are opened toward the centers of the wafers 200 in plane view, soas to allow a gas to be supplied toward the wafers 200. The gas supplyholes 250 a and 250 b may be formed in a plural number between the lowerportion of the reaction tube 203 and the upper portion of the reactiontube 203.

A precursor gas, for example, a halosilane-based gas which containssilicon (Si) as a main element (predetermined element) constituting afilm and a halogen element, is supplied from the gas supply pipe 232 ainto the process chamber 201 via the MFC 241 a, the valve 243 a, and thenozzle 249 a. The precursor gas refers to a gaseous precursor, forexample, a gas obtained by vaporizing a precursor which remains in aliquid state under a room temperature and an atmospheric pressure, or aprecursor which remains in a gas state under a room temperature and anatmospheric pressure. The halosilane refers to a silane containing ahalogen element. The halogen element contains chlorine (Cl), fluorine(F), bromine (Br), iodine (I), or the like. As the halosilane-based gas,it may be possible to use, for example, a precursor gas containing Siand Cl, i.e., a chlorosilane-based gas. The chlorosilane-based gas actsas a Si source. As the chlorosilane-based gas, it may be possible touse, for example, a hexachlorodisilane (Si₂Cl₆, abbreviation: HCDS) gas.The HCDS gas is a gas containing an element (Si) which becomes a solidalone under the aforementioned processing conditions, i.e., a gas whichcan deposit a film alone under the aforementioned processing conditions.

An oxygen (O)-containing gas as a reaction gas is supplied from the gassupply pipe 232 b into the process chamber 201 via the MFC 241 b, thevalve 243 b, and the nozzle 249 b. The O-containing gas acts as an Osource. As the O-containing gas, it may be possible to use, for example,an oxygen (O₂) gas.

A carbon (C)-containing gas as the reaction gas is supplied from the gassupply pipe 232 c into the process chamber 201 via the MFC 241 c, thevalve 243 c, the gas supply pipe 232 a, and the nozzle 249 a. TheC-containing gas acts as a C source. As the C-containing gas, it may bepossible to use, for example, a propylene (C₃H₆) gas which is ahydrocarbon-based gas.

A nitrogen (N)- and hydrogen (H)-containing gas as the reaction gas issupplied from the gas supply pipe 232 d into the process chamber 201 viathe MFC 241 d, the valve 243 d, the gas supply pipe 232 b, and thenozzle 249 b. The N- and H-containing gas acts as a N source. As the N-and H-containing gas, it may be possible to use, for example, an ammonia(NH₃) gas which is a hydrogen nitride-based gas.

A cleaning gas is supplied from the gas supply pipes 232 e and 232 finto the process chamber 201 via the MFCs 241 e and 241 f, the valves243 e and 243 f, the gas supply pipes 232 a and 232 b, and the nozzles249 a and 249 b. The cleaning gas acts as a cleaning gas in each ofchamber cleaning, first nozzle cleaning, and second nozzle cleaning,which will be described later. As the cleaning gas, it may be possibleto use, for example, a fluorine (F₂) gas.

A nitric oxide-based gas as an additive gas is supplied from the gassupply pipe 232 g into the process chamber 201 via the MFC 241 g, thevalve 243 g, the gas supply pipe 232 b, and the nozzle 249 b. The nitricoxide-based gas alone does not exert a cleaning action, but acts toimprove the cleaning action of the cleaning gas by reacting with thecleaning gas in the chamber cleaning as described hereinbelow togenerate active species such as, e.g., fluorine radicals, nitrosylhalide compounds, or the like. As the nitric oxide-based gas, it may bepossible to use, for example, a nitrogen monoxide (NO) gas.

An inert gas, for example, a nitrogen (N₂) gas, is supplied from the gassupply pipes 232 h and 232 i into the process chamber 201 via the MFC241 h and 241 i, the valves 243 h and 243 i, the gas supply pipes 232 aand 232 b, and the nozzles 249 a and 249 b. The N₂ gas acts as a purgegas, a carrier gas, a dilution gas, or the like.

A precursor gas supply system mainly includes the gas supply pipe 232 a,the MFC 241 a, the valve 243 a, and the nozzle 249 a. An O-containinggas supply system mainly includes the gas supply pipe 232 b, the MFC 241b, the valve 243 b, and the nozzle 249 b. A C-containing gas supplysystem mainly includes the gas supply pipe 232 c, the MFC 241 c, thevalve 243 c, the gas supply pipe 232 a, and the nozzle 249 a. A N- andH-containing gas supply system mainly includes the gas supply pipe 232d, the MFC 241 d, the valve 243 d, the gas supply pipe 232 b, and thenozzle 249 b. A cleaning gas supply system mainly includes the gassupply pipes 232 e and 232 f, the MFCs 241 e and 241 f, and the valve243 e and 243 f The gas supply pipes 232 a and 232 b and the nozzles 249a and 249 b may be regarded as being included in the cleaning gas supplysystem. An additive gas supply system mainly includes the gas supplypipe 232 g, the MFC 241 g, the valve 243 g, the gas supply pipe 232 b,and the nozzle 249 b. An inert gas supply system mainly includes the gassupply pipes 232 h and 232 i, the MFCs 241 h and 241 i, the valve 243 hand 243 i, the gas supply pipes 232 a and 232 b, and the nozzles 249 aand 249 b.

One or more of various supply systems described above may be configuredas an integrated supply system 248 in which the valves 243 a to 243 i,the MFCs 241 a to 241 i, and the like are integrated. The integratedsupply system 248 is connected to each of the gas supply pipes 232 a to232 i so that a supply operation of various kinds of gases into the gassupply pipes 232 a to 232 i, i.e., an opening/closing operation of thevalves 243 a to 243 i, a flow-rate-adjusting operation by the MFCs 241 ato 241 i or the like, is controlled by a controller 121 which will bedescribed later. The integrated supply system 248 is configured as anintegral type or division type integrated unit, and is also configuredso that it is detachable from the gas supply pipes 232 a to 232 i or thelike, so as to perform maintenance, replacement, expansion, or the likeof the integrated supply system 248, on an integrated unit basis.

An exhaust port 231 a configured to exhaust an internal atmosphere ofthe process chamber 201 is installed at a lower side of the sidewall ofthe reaction tube 203. The exhaust port 231 a may be installed betweenthe lower portion of the sidewall of the reaction tube 203 and the upperportion thereof, i.e., along the wafer arrangement region. An exhaustpipe 231 is connected to the exhaust port 231 a. The exhaust pipe 231 ismade of a metal material such as, e.g., stainless steel (SUS) or thelike. A vacuum pump 246 as a vacuum exhaust device is connected to theexhaust pipe 231 via a pressure sensor 245 as a pressure detector(pressure detection part) which detects the internal pressure of theprocess chamber 201 and an APC (auto pressure controller) valve 244 as apressure regulator (pressure regulation part). The APC valve 244 isconfigured so that a vacuum exhaust and a vacuum exhaust stop of theinterior of the process chamber 201 can be performed by opening andclosing the APC valve 244 while operating the vacuum pump 246 and sothat the internal pressure of the process chamber 201 can be adjusted byadjusting an opening degree of the APC valve 244 based on pressureinformation detected by the pressure sensor 245 while operating thevacuum pump 246. An exhaust system mainly includes the exhaust pipe 231,the APC valve 244, and the pressure sensor 245. The vacuum pump 246 maybe regarded as being included in the exhaust system.

A seal cap 219, which serves as a furnace opening cover configured tohermetically seal a lower end opening of the manifold 209, is installedunder the manifold 209. The seal cap 219 is made of a metal materialsuch as, e.g., stainless steel (SUS) or the like, and is formed in adisc shape. An O-ring 220 b, which is a seal member making contact withthe lower end portion of the manifold 209, is installed at an uppersurface of the seal cap 219.

A rotator 267 configured to rotate a boat 217, which will be describedlater, is installed under the seal cap 219. A rotary shaft 255 of therotator 267, which is made of a metal material such as stainless steelor the like and penetrates the seal cap 219, is connected to the boat217. The rotator 267 is configured to rotate the wafers 200 by rotatingthe boat 217. The seal cap 219 is configured to be vertically moved upand down by a boat elevator 115 which is an elevator mechanism installedoutside the reaction tube 203. The boat elevator 115 is configured as atransfer device (transfer mechanism) which loads and unloads (transfers)the wafers 200 into and from (out of) the process chamber 201 by movingthe seal cap 219 up and down.

A shutter 219 s as a furnace opening cover capable of hermetically sealthe lower end opening of the manifold 209, with the boat 217 unloadedfrom the interior of the process chamber 201 by moving the seal cap 219down, is installed under the manifold 209. The shutter 219 s is made ofa metal material such as, e.g., stainless steel or the like, and isformed in a disc shape. An O-ring 220 c as a seal member making contactwith the lower end portion of the manifold 209 is installed at an uppersurface of the shutter 219 s. An opening/closing operation (an up-downmovement operation or a rotational movement operation) of the shutter219 s is controlled by a shutter-opening/closing mechanism 115 s.

The boat 217 serving as a substrate support is configured to support aplurality of wafers 200, e.g., 25 to 200 wafers, in such a state thatthe wafers 200 are arranged in a horizontal posture and in multiplestages along a vertical direction with the centers of the wafers 200aligned with one another. That is, the boat 217 is configured to arrangethe wafers 200 in a spaced-apart relationship. The boat 217 is composedof a heat resistant material such as quartz or SiC. Heat-insulatingplates 218 composed of a heat resistant material such as quartz or SiCare installed below the boat 217 in multiple stages.

A temperature sensor 263 serving as a temperature detector is installedin the reaction tube 203. Based on temperature information detected bythe temperature sensor 263, a degree of supplying electric power to theheater 207 is adjusted such that the interior of the process chamber 201has a desired temperature distribution. The temperature sensor 263 isinstalled along the inner wall of the reaction tube 203.

As illustrated in FIG. 3, the controller 121, which is a control part(control means), may be configured as a computer including a CPU(central processing unit) 121 a, a RAM (random access memory) 121 b, amemory 121 c, and an I/O port 121 d. The RAM 121 b, the memory 121 c,and the I/O port 121 d are configured to exchange data with the CPU 121a via an internal bus 121 e. An input/output device 122 formed of, e.g.,a touch panel or the like, is connected to the controller 121.

The memory 121 c is configured by, for example, a flash memory, a HDD(hard disk drive), or the like. A control program for controllingoperations of a substrate processing apparatus, a process recipe forspecifying sequences and conditions of a film-forming process asdescribed hereinbelow, a cleaning recipe for specifying sequences andconditions of a cleaning process as described hereinbelow, or apre-coating recipe for specifying sequences and conditions of apre-coating process as described hereinbelow is readably stored in thememory 121 c. The process recipe functions as a program for causing thecontroller 121 to execute each sequence in the film-forming process, asdescribed hereinbelow, to obtain a predetermined result. The cleaningrecipe functions as a program for causing the controller 121 to executeeach sequence in the cleaning process, as described hereinbelow, toobtain a predetermined result. The pre-coating recipe functions as aprogram for causing the controller 121 to execute each sequence in thepre-coating process, as described hereinbelow, to obtain a predeterminedresult. Hereinafter, the process recipe, the cleaning recipe, thepre-coating recipe, and the control program will be generally and simplyreferred to as a “program.” Furthermore, the process recipe, thecleaning recipe, and the pre-coating recipe will be simply referred toas a “recipe.” When the term “program” is used herein, it may indicate acase of including the recipe, a case of including the control program,or a case of including both the recipe and the control program. The RAM121 b is configured as a memory area (work area) in which a program,data, and the like read by the CPU 121 a is temporarily stored.

The I/O port 121 d is connected to the MFCs 241 a to 241 i, the valves243 a to 243 i, the pressure sensor 245, the APC valve 244, the vacuumpump 246, the temperature sensor 263, the heater 207, the rotator 267,the boat elevator 115, the shutter-opening/closing mechanism 115 s, andthe like, as described above.

The CPU 121 a is configured to read the control program from the memory121 c and execute the same. The CPU 121 a is also configured to read therecipe from the memory 121 c according to an input of an operationcommand from the input/output device 122. In addition, the CPU 121 a isconfigured to control, according to the contents of the recipe thusread, the flow-rate-adjusting operation of various kinds of gases by theMFCs 241 a to 241 i, the opening/closing operation of the valves 243 ato 243 i, the opening/closing operation of the APC valve 244, thepressure-regulating operation performed by the APC valve 244 based onthe pressure sensor 245, the driving and stopping of the vacuum pump246, the temperature-adjusting operation performed by the heater 207based on the temperature sensor 263, the operations of rotating the boat217 and adjusting the rotation speed of the boat 217 with the rotator267, the operation of moving the boat 217 up and down with the boatelevator 115, the operations of opening and closing the shutter 219 swith the shutter-opening/closing mechanism 115 s, and the like.

The controller 121 may be configured by installing, on the computer, theaforementioned program stored in an external memory 123. The externalmemory 123 may include, for example, a magnetic disc such as a HDD, anoptical disc such as a CD, a magneto-optical disc such as a MO, asemiconductor memory such as a USB memory, and the like. The memory 121c or the external memory 123 is configured as a non-transitorycomputer-readable recording medium. Hereinafter, the memory 121 c andthe external memory 123 will be generally and simply referred to as a“recording medium.” When the term “recording medium” is used herein, itmay indicate a case of including the memory 121 c, a case of includingthe external memory 123, or a case of including both the memory 121 cand the external memory 123. Furthermore, the program may be supplied tothe computer using a communication means such as the Internet or adedicated line, instead of using the external memory 123.

(2) Substrate Processing

An example of a series of processing sequences including a film-formingsequence of forming a film on a wafer 200 as a substrate using theaforementioned substrate processing apparatus, which is one of theprocesses for manufacturing a semiconductor device, will be describedmainly with reference to FIGS. 4 and 5. In the following descriptions,the operations of the respective parts constituting the substrateprocessing apparatus are controlled by the controller 121.

In the series of processing sequences illustrated in FIG. 4, there areperformed: a step of forming a SiOCN film which is an oxycarbonitridefilm as a film on a wafer 200 by supplying a first processing gas to thewafer 200 in the process container; a step of removing depositsdeposited in the process container by supplying a cleaning gas into theprocess container in a state in which the wafer 200 does not exist inthe process container; a step of forming a SiON film, which is anoxynitride film as a first pre-coated film having a first thickness andhaving a material different from that of the film formed on the wafer200, in the process container by supplying a second processing gas intothe process container in the state in which the wafer 200 does not existin the process container; and a step of forming a SiOCN film, which isan oxycarbonitride film as a second pre-coated film having a secondthickness smaller than the first thickness and having the same materialas that of the film formed on the wafer 200, on the SiON film formed inthe process container by supplying a third processing gas into theprocess container in the state in which the wafer 200 does not exist inthe process container.

In the present embodiments, a HCDS gas which is a Si source, a C₃H₆ gaswhich is a C source, an O₂ gas which is an O source, and an NH₃ gaswhich is a N source are used as the first processing gas. Furthermore, aHCDS gas which is a Si source, an O₂ gas which is an O source, and anNH₃ gas which is a N source are used as the second processing gas. Inaddition, a HCDS gas which is a Si source, a C₃H₆ gas which is a Csource, an O₂ gas which is an O source, and an NH₃ gas which is a Nsource are used as the third processing gas.

In the film-forming process of the present embodiments, as illustratedin the gas supply sequence in FIG. 5, a SiOCN film is formed on thewafer 200 by implementing a cycle a predetermined number of times (ntimes, where n is an integer of 1 or more), the cycle includingsequentially and non-simultaneously performing: step 1 of supplying aHCDS gas to the wafer 200 in the process container; step 2 of supplyinga C₃H₆ gas to the wafer 200 in the process container; step 3 ofsupplying an O₂ gas to the wafer 200 in the process container; and step4 of supplying an NH₃ gas to the wafer 200 in the process container.

In the present disclosure, for the sake of convenience, the gas supplysequence illustrated in FIG. 5, i.e., the film-forming sequence, maysometimes be denoted as follows. The same denotation will be used inother embodiments as described hereinbelow.(HCDS→C₃H₆→O₂→NH₃)×n=SiOCN

When the term “wafer” is used herein, it may refer to a wafer itself ora laminated body of a wafer and a predetermined layer or film formed onthe surface of the wafer. In addition, when the phrase “a surface of awafer” is used herein, it may refer to a surface of a wafer itself or asurface of a predetermined layer or the like formed on a wafer.Furthermore, in the present disclosure, the expression “a predeterminedlayer is formed on a wafer” may mean that a predetermined layer isdirectly formed on a surface of a wafer itself or that a predeterminedlayer is formed on a layer or the like formed on a wafer. In addition,when the term “substrate” is used herein, it may be synonymous with theterm “wafer.”

Hereinafter, the series of processing sequences illustrated in FIG. 4will be described in detail.

<Film-Forming Process>

First, a film-forming process of forming a film on the wafer 200 isperformed. Hereinafter, a series of operations of the film-formingprocess will be described.

(Wafer Charging and Boat Loading)

If a plurality of wafers 200 is charged on the boat 217 (wafercharging), the shutter 219 s may be moved by the shutter-opening/closingmechanism 115 s to open the lower end opening of the manifold 209(shutter opening). Thereafter, as illustrated in FIG. 1, the boat 217supporting the plurality of wafers 200 is lifted up by the boat elevator115 and is loaded into the process chamber 201 (boat loading). In thisstate, the seal cap 219 seals the lower end of the manifold 209 via theO-ring 220 b.

(Pressure Regulation and Temperature Adjustment)

The interior of the process chamber 201, namely the space in which thewafers 200 are located, is vacuum-exhausted (depressurization-exhausted)by the vacuum pump 246 so as to reach a desired pressure (film-formingpressure). Furthermore, the wafers 200 in the process chamber 201 areheated by the heater 207 to a desired temperature (film-formingtemperature). In addition, the rotation of the wafers 200 by the rotator267 begins. The exhaust of the interior of the process chamber 201 andthe heating and rotation of the wafers 200 may be continuously performedat least until the process to the wafers 200 is completed.

(Film Formation)

Next, the following steps 1 to 4 are sequentially performed.

[Step 1]

At this step, a HCDS gas is supplied to the wafer 200 in the processcontainer (HCDS gas supply). Specifically, the valve 243 a is opened toallow an HCDS gas to flow through the gas supply pipe 232 a. The flowrate of the HCDS gas is adjusted by the MFC 241 a. The HCDS gas issupplied into the process chamber 201 via the nozzle 249 a and isexhausted from the exhaust port 231 a. At this time, the HCDS gas issupplied to the wafer 200. Simultaneously, the valves 243 h and 243 imay be opened to supply a N₂ gas into the process chamber 201 via thenozzles 249 a and 249 b.

The processing conditions at this step may be exemplified as follows:

HCDS gas supply flow rate: 0.01 to 2 slm or 0.1 to 1 slm in someembodiments

N₂ gas supply flow rate (per gas supply pipe): 0 to 10 slm

Supply time of each gas: 1 to 120 seconds or 1 to 60 seconds in someembodiments

Processing temperature: 250 to 800 degrees C. or 400 to 700 degrees C.in some embodiments

Processing pressure: 1 to 2,666 Pa or 67 to 1,333 Pa in someembodiments.

Furthermore, in the present disclosure, the expression of the numericalrange such as “250 to 800 degrees C.” may mean that a lower limit valueand an upper limit value are included in that range. Therefore, forexample, “250 to 800 degrees C.” may mean “250 degrees C. or higher and800 degrees C. or lower.” The same applies to other numerical ranges.

By supplying the HCDS gas to the wafer 200 under the aforementionedconditions, a Si-containing layer containing Cl is formed as a firstlayer on the outermost surface of the wafer 200. The Si-containing layercontaining Cl is formed by physisorption of HCDS, chemisorption of HCDSor a substance (hereinafter, Si_(x)Cl_(y)) obtained by partiallydecomposing HCDS, deposition of Si by pyrolysis of HCDS, or the like, tothe outermost surface of the wafer 200. The Si-containing layercontaining Cl may be an adsorption layer (a physisorption layer or achemisorption layer) of HCDS or Si_(x)Cl_(y), or may be a deposit layerof Si containing Cl. In the present disclosure, the Si-containing layercontaining Cl will be simply referred to as a Si-containing layer.

After the first layer is formed, the valve 243 a is closed to stop thesupply of the HCDS gas into the process chamber 201. Then, the interiorof the process chamber 201 is vacuum-exhausted and the gas or the likeremaining within the process chamber 201 is removed from the interior ofthe process chamber 201 (purge). At this time, the valves 243 h and 243i are opened to supply a N₂ gas into the process chamber 201. The N₂ gasacts as a purge gas.

As the precursor gas, it may be possible to use, in addition to the HCDSgas, a chlorosilane-based gas such as a monochlorosilane (SiH₃Cl,abbreviation: MCS) gas, a dichlorosilane (SiH₂Cl₂, abbreviation: DCS)gas, a trichlorosilane (SiHCl₃, abbreviation: TCS) gas, atetrachlorosilane (SiCl₄, abbreviation: STC) gas, an octachlorotrisilane(Si₃Cl₈, abbreviation: OCTS) gas, or the like.

[Step 2]

After step 1 is completed, a C₃H₆ gas is supplied to the wafer 200 inthe process container, namely the first layer formed on the wafer 200(C₃H₆ gas supply). Specifically, the valve 243 c is opened to allow aC₃H₆ gas to flow through the gas supply pipe 232 c. The flow rate of theC₃H₆ gas is adjusted by the MFC 241 c. The C₃H₆ gas is supplied into theprocess chamber 201 via the gas supply pipe 232 a and the nozzle 249 aand is exhausted from the exhaust port 231 a. At this time, the C₃H₆ gasis supplied to the wafer 200. Simultaneously, the valves 243 h and 243 imay be opened to supply a N₂ gas into the process chamber 201 via thenozzles 249 a and 249 b.

The processing conditions at this step may be exemplified as follows:

C₃H₆ gas supply flow rate: 0.1 to 10 slm

Supply time of C₃H₆ gas: 1 to 120 seconds or 1 to 60 seconds in someembodiments

Processing pressure: 1 to 6,000 Pa or 1 to 5,000 Pa in some embodiments.

Other processing conditions may be similar to the processing conditionsof step 1.

By supplying the C₃H₆ gas to the wafer 200 under the aforementionedconditions, a C-containing layer is formed on the first layer to form asecond layer containing Si and C on the wafer 200.

After the second layer is formed, the valve 243 c is closed to stop thesupply of the C₃H₆ gas into the process chamber 201. Then, the gas orthe like, which remains within the process chamber 201, is removed fromthe interior of the process chamber 201 according to the same processingprocedures as those of the purge at step 1 (purge).

As the reaction gas (C-containing gas), it may be possible to use, inaddition to the C₃H₆ gas, a hydrocarbon-based gas such as an acetylene(C₂H₂) gas, an ethylene (C₂H₄) gas, or the like.

[Step 3]

After step 2 is completed, an O₂ gas is supplied to the wafer 200 in theprocess container, namely the second layer formed on the wafer 200 (O₂gas supply). Specifically, the valve 243 b is opened to allow an O₂ gasto flow through the gas supply pipe 232 b. The flow rate of the O₂ gasis adjusted by the MFC 241 b. The O₂ gas is supplied into the processchamber 201 via the nozzle 249 b and is exhausted from the exhaust port231 a. At this time, the O₂ gas is supplied to the wafer 200.Simultaneously, the valves 243 h and 243 i may be opened to supply a N₂gas into the process chamber 201 via the nozzles 249 a and 249 b.

The processing conditions at this step may be exemplified as follows:

O₂ gas supply flow rate: 0.1 to 10 slm

Supply time of O₂ gas: 1 to 120 seconds or 1 to 60 seconds in someembodiments

Processing pressure: 1 to 4,000 Pa or 1 to 3,000 Pa in some embodiments.

Other processing conditions may be similar to the processing conditionsof step 1.

By supplying the O₂ gas to the wafer 200 under the aforementionedconditions, at least a portion of the second layer formed on the wafer200 is oxidized (modified). By modifying the second layer, a third layercontaining Si, O, and C, i.e., a silicon oxycarbide layer (SiOC layer),is formed on the wafer 200. When forming the third layer, an impuritysuch as Cl contained in the second layer constitutes a gaseous substancecontaining at least Cl in the process of the modification reaction ofthe second layer with the O₂ gas and is exhausted from the interior ofthe process chamber 201. Thus, the third layer becomes a layer having asmaller amount of impurity such as Cl than the first and second layers.

After the third layer is formed, the valve 243 b is closed to stop thesupply of the O₂ gas into the process chamber 201. Then, the gas or thelike, which remains within the process chamber 201, is removed from theprocess chamber 201 according to the same processing procedures as thoseof the purge at step 1 (purge).

As the reaction gas (O-containing gas), it may be possible to use, inaddition to the O₂ gas, for example, an ozone (O₃) gas, water vapor (H₂Ogas), a nitric oxide (NO) gas, a nitrous oxide (N₂O) gas, or the like.

[Step 4]

After step 3 is completed, an NH₃ gas is supplied to the wafer 200 inthe process container, namely the third layer formed on the wafer 200(NH₃ gas supply). Specifically, the valve 243 d is opened to allow anNH₃ gas to flow through the gas supply pipe 232 d. The flow rate of theNH₃ gas is adjusted by the WC 241 d. The NH₃ gas is supplied into theprocess chamber 201 via the gas supply pipe 232 b and the nozzle 249 band is exhausted from the exhaust port 231 a. At this time, the NH₃ gasis supplied to the wafer 200. Simultaneously, the valves 243 h and 243 imay be opened to supply a N₂ gas into the process chamber 201 via thenozzles 249 a and 249 b.

The processing conditions at this step may be exemplified as follows:

NH₃ gas supply flow rate: 0.1 to 10 slm

Supply time of NH₃ gas: 1 to 120 seconds or 1 to 60 seconds in someembodiments

Processing pressure: 1 to 4,000 Pa or 1 to 3,000 Pa in some embodiments.

Other processing conditions may be similar to the processing conditionsof step 1.

By supplying the NH₃ gas to the wafer 200 under the aforementionedconditions, at least a portion of the third layer formed on the wafer200 is nitrided (modified). By modifying the third layer, a fourth layercontaining Si, O, C, and N, i.e., a silicon oxycarbonitride layer (SiOCNlayer), is formed on the wafer 200. When forming the fourth layer, animpurity such as Cl contained in the third layer constitutes a gaseoussubstance containing at least Cl in the process of the modificationreaction of the third layer with the NH₃ gas and is exhausted from theinterior of the process chamber 201. Thus, the fourth layer becomes alayer having a smaller amount of impurity such as Cl than the thirdlayer.

After the fourth layer is formed, the valve 243 d is closed to stop thesupply of the NH₃ gas into the process chamber 201. Then, the gas or thelike, which remains within the process chamber 201, is removed from theinterior of the process chamber 201 according to the same processingprocedures as those of the purge at step 1 (purge).

As the reaction gas (N- and H-containing gas), it may be possible touse, in addition to the NH₃ gas, for example, a hydrogen nitride-basedgas such as a diazene (N₂H₂) gas, a hydrazine (N₂H₄) gas, a N₃H₈ gas, orthe like.

[Performing a Predetermined Number of Times]

A cycle which non-simultaneously, i.e., non-synchronously, performssteps 1 to 4 described above is implemented a predetermined number oftimes (n times, where n is an integer of 1 or more), whereby a siliconoxycarbonitride film (SiOCN film) which is a film containing Si, O, Cand N and having a predetermined composition and a predetermined filmthickness can be formed on the wafer 200. The aforementioned cycle maybe repeated multiple times.

(After-Purge and Atmospheric Pressure Return)

After the film formation is completed, the N₂ gas as a purge gas issupplied from each of the nozzles 249 a and 249 b into the processchamber 201 and is exhausted from the exhaust port 231 a. Thus, theinterior of the process chamber 201 is purged and the gas or thereaction byproduct, which remains within the process chamber 201, isremoved from the interior of the process chamber 201 (after-purge).Thereafter, the internal atmosphere of the process chamber 201 issubstituted by an inert gas (inert gas substitution). The internalpressure of the process chamber 201 is returned to an atmosphericpressure (atmospheric pressure return).

(Boat Unloading and Wafer Discharging)

The seal cap 219 is moved down by the boat elevator 115 to open thelower end of the manifold 209. Then, the processed wafers 200 supportedon the boat 217 are unloaded from the lower end of the manifold 209 tothe outside of the reaction tube 203 (boat unloading). After the boatunloading, the shutter 219 s is moved so that the lower end opening ofthe manifold 209 is sealed by the shutter 219 s via the O-ring 220 c(shutter closing). The processed wafers 200 are unloaded to the outsideof the reaction tube 203 and are subsequently discharged from the boat217 (wafer discharging).

<Cleaning Process>

When the aforementioned film-forming process is performed, depositscontaining a thin film such as a SiOCN film are adhered to andaccumulated in the process container, i.e., on the surface of any memberin the process container such as the inner wall of the reaction tube203, the outer surfaces of the nozzles 249 a and 249 b, the innersurfaces of the nozzles 249 a and 249 b, the inner surface of themanifold 209, the surface of the boat 217, the upper surface of the sealcap 219, or the like. If the amount of deposits, i.e., the cumulativefilm thickness, becomes too large, the deposits may be delaminated,rapidly increasing the amount of particles generated. Therefore, acleaning process is performed to remove the deposits deposited in theprocess container before the cumulative film thickness (the amount ofdeposits) reaches a predetermined thickness (predetermined amount) priorto the occurrence of delamination or dropping of the deposits.Hereinafter, a series of operations of the cleaning process will bedescribed.

(Empty Boat Loading)

The shutter 219 s is moved by the shutter-opening/closing mechanism 115s to open the lower end opening of the manifold 209 (shutter opening).Thereafter, the empty boat 217, i.e., the boat 217 with no wafer 200charged, is lifted up by the boat elevator 115 and is loaded into theprocess chamber 201. In this state, the seal cap 219 seals the lower endof the manifold 209 via the O-ring 220 b.

(Pressure Regulation and Temperature Adjustment)

After the loading of the empty boat 217 into the process chamber 201 iscompleted, the interior of the process chamber 201 is vacuum-exhaustedby the vacuum pump 246 so as to reach a desired pressure(chamber-cleaning pressure). Furthermore, the interior of the processchamber 201 is heated by the heater 207 to a desired temperature(chamber-cleaning temperature). At this time, the surfaces of themembers in the process chamber 201 (in the process container), i.e., theinner wall of the reaction tube 203, the surfaces of the nozzles 249 aand 249 b, the surface of the boat 217, and the like, are also heated tothe chamber-cleaning temperature. In addition, the rotation of the boat217 by the rotator 267 begins. The driving of the vacuum pump 246, theheating of the interior of the process chamber 201, and the rotation ofthe boat 217 may be continuously performed at least until the nozzlecleaning as described hereinbelow is completed. The boat 217 may alsonot be rotated.

(Chamber Cleaning)

After the internal pressure and temperature of the process chamber 201are stabilized, the interior of the process chamber 201 is cleaned bysupplying a F₂ gas and a NO gas into the process chamber 201.Specifically, the valves 243 e and 243 g are opened to allow a F₂ gas toflow through the gas supply pipe 232 e and to allow a NO gas to flowthrough the gas supply pipe 232 g. The flow rates of the F₂ gas and theNO gas are adjusted by the MFCs 241 e and 241 g, respectively. The F₂gas and the NO gas are supplied into the process chamber 201 via the gassupply pipes 232 a and 232 b and the nozzles 249 a and 249 b and areexhausted from the exhaust port 231 a. Simultaneously, the valves 243 hand 243 i may be opened to supply a N₂ gas into the process chamber 201via the nozzles 249 a and 249 b.

The processing conditions at this step may be exemplified as follows:

F₂ gas supply flow rate: 0.5 to 10 slm

NO gas supply flow rate: 0.5 to 10 slm

N₂ gas supply flow rate (per gas supply pipe): 0 to 10 slm

Supply time of each gas: 1 to 60 minutes or 10 to 20 minutes in someembodiments

Processing temperature (chamber-cleaning temperature): 100 to 350degrees C. or 200 to 300 degrees C. in some embodiments

Processing pressure (chamber-cleaning pressure): 1,333 to 53,329 Pa or9,000 to 16,665 Pa in some embodiments.

By supplying the F₂ gas and the NO gas into the process chamber 201under the aforementioned processing conditions, the NO gas can be addedto the F₂ gas, and these gases can be mixed and reacted in the processchamber 201. By this reaction, active species such as, e.g., fluorineradicals (F*) or nitrosyl fluoride (FNO) (hereinafter, these will begenerally referred to as FNO or the like), can be generated in theprocess chamber 201. As a result, a mixture gas obtained by adding FNOor the like to the F₂ gas exists in the process chamber 201. The mixturegas obtained by adding FNO or the like to the F₂ gas is brought intocontact with the surfaces of the members in the process chamber 201, forexample, the inner wall of the reaction tube 203, the surfaces of thenozzles 249 a and 249 b, the surface of the boat 217, and the like. Atthis time, deposits on the surface of any member in the process chamber201 can be removed by a thermochemical reaction (etching reaction). TheFNO or the like acts to promote the etching reaction by the F₂ gas andto increase the etching rate of the deposits, i.e., acts to assist theetching.

After a predetermined time elapses and the cleaning of the interior ofthe process chamber 201 is completed, the valves 243 e and 243 g areclosed to stop the supply of the F₂ gas and the NO gas into the processchamber 201. Then, the interior of the process chamber 201 isvacuum-exhausted and the gas or the like remaining within the processchamber 201 is removed from the interior of the process chamber 201(purge). At this time, the valves 243 h and 243 i are opened to supply aN₂ gas into the process chamber 201. The N₂ gas acts as a purge gas.

As the cleaning gas, it may be possible to use, in addition to the F₂gas, a hydrogen fluoride (HF) gas, a nitrogen fluoride (NF₃) gas, achlorine fluoride (ClF₃) gas, or a mixture gas thereof. This alsoapplies to the nozzle cleaning as described hereinbelow.

As the additive gas, it may be possible to use, in addition to the NOgas, a hydrogen (H₂) gas, an O₂ gas, a nitrous oxide (N₂O) gas, anisopropyl alcohol ((CH₃)₂CHOH, abbreviation: IPA) gas, a methanol(CH₃OH) gas, water vapor (H₂O gas), a HF gas, or a mixture gas thereof.

Furthermore, when the HF gas is used as the additive gas, one of the F₂gas, the ClF₃ gas, the NF₃ gas, and a mixture gas thereof may be used asthe cleaning gas. In addition, when the HF gas is used as the cleaninggas and one of the IPA gas, the methanol gas, the H₂O gas, and a mixturegas thereof is used as the additive gas, it is desirable that theaforementioned processing temperature be set at a predeterminedtemperature which falls within a range of, for example, 30 to 300degrees C. or 50 to 200 degrees C. in some embodiments.

As the inert gas, it may be possible to use, in addition to the N₂ gas,a rare gas such as an Ar gas, a He gas, a Ne gas, a Xe gas, or the like.This also applies to each step as described hereinbelow.

(Pressure Regulation and Temperature Adjustment)

After the chamber cleaning is completed, the interior of the processchamber 201 is vacuum-exhausted by the vacuum pump 246 so as to reach adesired pressure (nozzle-cleaning pressure). Furthermore, the interiorof the nozzles 249 a and 249 b is heated by the heater 207 to a desiredtemperature (nozzle-cleaning temperature).

(First Nozzle Cleaning)

After the interior pressure of the process chamber 201 and the internaltemperature of the nozzles 249 a and 249 b are stabilized, the interiorof the nozzle 249 a is cleaned by supplying a F₂ gas into the nozzle 249a. Specifically, the valve 243 e is opened to allow a F₂ gas to flowthrough the gas supply pipe 232 e. The flow rate of the F₂ gas isadjusted by the MFC 241 e. The F₂ gas is supplied into the nozzle 249 avia the gas supply pipe 232 a to flow through the process chamber 201and is exhausted from the exhaust port 231 a. Simultaneously, the valves243 h and 243 i may be opened to supply a N₂ gas into the processchamber 201 via the nozzles 249 a and 249 b.

The processing conditions at this step may be exemplified as follows:

F₂ gas supply flow rate: 0.5 to 10 slm

N₂ gas supply flow rate (per gas supply pipe): 0 to 10 slm

Supply time of each gas: 1 to 60 minutes or 10 to 20 minutes in someembodiments

Processing temperature (nozzle-cleaning temperature): 400 to 500 degreesC. or 400 to 450 degrees C. in some embodiments

Processing pressure (nozzle-cleaning pressure): 1,333 to 40,000 Pa or6,666 to 16,665 Pa in some embodiments.

By supplying the F₂ gas into the nozzle 249 a under the aforementionedprocessing conditions, deposits in the nozzle 249 a can be removed by athermochemical reaction. After a predetermined time elapses and thecleaning of the interior of the nozzle 249 a is completed, the valve 243e is closed to stop the supply of the F₂ gas into the nozzle 249 a.Then, the interior of the process chamber 201 is purged in the sameprocessing procedure as that of the purge in the chamber cleaningdescribed above (purge).

(Second Nozzle Cleaning)

After the cleaning of the interior of the nozzle 249 a is completed, theinterior of the nozzle 249 b is cleaned by supplying an F₂ gas into thegas supply pipe 232 b. Specifically, the valve 243 f is opened to allowan F₂ gas to flow through the gas supply pipe 232 f The flow rate of theF₂ gas is adjusted by the MFC 241 f. The F₂ gas is supplied into thenozzle 249 b via the gas supply pipe 232 b to flow through the processchamber 201 and is exhausted from the exhaust port 231 a.Simultaneously, the valves 243 h and 243 i may be opened to supply a N₂gas into the process chamber 201 via the nozzles 249 a and 249 b.

The processing conditions at this step may be similar to the processingconditions in the first nozzle cleaning described above.

By supplying the F₂ gas into the nozzle 249 b under the aforementionedprocessing conditions, deposits in the nozzle 249 b can be removed by athermochemical reaction. After a predetermined time elapses and thecleaning of the interior of the nozzle 249 b is completed, the valve 243f is closed to stop the supply of the F₂ gas into the nozzle 249 b.Then, the interior of the process chamber 201 is purged in the sameprocessing procedure as that of the purge in the chamber cleaningdescribed above (purge). Thereafter, the internal atmosphere of theprocess chamber 201 is substituted by an inert gas (inert gassubstitution). By the series of operations described above, the cleaningprocess is completed.

<Pre-Coating Process>

After the cleaning process is completed and before the boat unloading isperformed, i.e., in a state in which the empty boat is loaded into theprocess container, a pre-coating process is performed in the processcontainer, i.e., on the surfaces of the members in the process containersuch as the inner wall of the reaction tube 203, the outer surfaces ofthe nozzles 249 a and 249 b, the inner surfaces of the nozzles 249 a and249 b, the inner surface of the manifold 209, the surface of the boat217, the upper surface of the seal cap 219, and the like.

After the cleaning process, if the film-forming process is performed inthe process container without performing the pre-coating process, theremay be a case where a film thickness drop phenomenon in which thethickness of the film formed on the wafer 200 becomes smaller than atarget film thickness occurs. This may be considered to be because thestate of the interior of the process container after the cleaningprocess is different from the state of the interior of the processcontainer when the film-forming process is repeatedly performed, andthus, the processing gas is consumed on the surface of any member in theprocess container during the film-forming process, making the amount ofthe processing gas supplied to the surface of the wafer 200insufficient. By performing the pre-coating process after the cleaningprocess and before the film-forming process, it is possible to suppressthe occurrence of the film thickness drop phenomenon and to stabilizethe film thickness of the film formed on the wafer 200. A series ofoperations of the pre-coating process will be described below.

(First Pre-coating)

In a state in which the wafer 200 does not exist in the processcontainer, a cycle which sequentially and non-simultaneously performsthe same steps as step 1, step 3, and step 4 in the aforementioned filmformation in the process container is implemented a predetermined numberof times (x times, where x is an integer of 1 or more). The processingprocedures and processing conditions at each step may be similar to theprocessing procedures and processing conditions in the aforementionedfilm formation, except that each gas is supplied into the processcontainer, instead of being supplied to the wafer 200. Thus, a filmcontaining Si, O, and N, i.e., a silicon oxynitride film (SiON film), isformed as a first pre-coated film in the process container, i.e., on thesurface of any member in the process container. In first pre-coating, aSiON film having a first thickness is formed in the process container.It is desirable that the thickness (first thickness) of the firstpre-coated film (SiON film) be set at a thickness which falls within arange of, for example, 150 Å or more and 350 Å or less or 200 Å or moreand 300 Å or less in some embodiments.

The first pre-coated film (SiON film) is a C-free film, and has adifferent material, i.e., a different molecular structure, from that ofthe film (SiOCN film) formed on the wafer 200. Furthermore, the firstpre-coated film (SiON film) contains no element other than the elements(Si, O, C, and N) contained in the film (SiOCN film) formed on the wafer200.

(Second Pre-Coating)

After the SiON film having the first thickness is formed in the processcontainer, i.e., on the surface of any member in the process container,by the first pre-coating, a cycle which sequentially andnon-simultaneously performs the same steps as steps 1 to 4 in theaforementioned film formation in the process container is implemented apredetermined number of times (y times, where y is an integer of 1 ormore) in a state in which the wafer 200 does not exist in the processcontainer. The processing procedures and processing conditions at eachstep may be similar to the processing procedures and processingconditions in the aforementioned film formation, except that each gas issupplied into the process container, instead of being supplied to thewafer 200. Thus, a SiOCN film which is a film containing Si, O, C, and Nis formed as a second pre-coated film in the process container, i.e., onthe first pre-coated film (SiON film) formed on the surface of anymember in the process container. In second pre-coating, a SiOCN filmhaving a second thickness smaller than the thickness (first thickness)of the SiON film is formed on the SiON film formed in the processcontainer.

The second pre-coated film (SiOCN film) is a C-containing film, and hasthe same material as that of the film (SiOCN film) formed on the wafer200. That is, the second pre-coated film (SiOCN film) contains noelement other than the elements (Si, O, C, and N) contained in the film(SiOCN film) formed on the wafer 200.

In other words, both the first pre-coated film (SiON film) and thesecond pre-coated film (SiOCN film) contain no element other than theelements contained in the film (SiOCN film) formed on the wafer 200.Therefore, since the processing gas in the film-forming process can beused in each pre-coating, the addition of a gas supply system forperforming the pre-coating is not required. Thus, it is possible toreduce the cost of the substrate processing apparatus. Hereinafter, afilm formed by laminating the second pre-coated film on the firstpre-coated film will be referred to as a pre-coated film.

The material of the second pre-coated film, which is the outermostsurface of the pre-coated film, needs to be equal to the material of thefilm formed on the wafer 200. This is because, when the wafer 200 isloaded into the process container and the SiOCN film is formed on thewafer 200 after the pre-coating, if the outermost surface of thepre-coated film formed in the process container is the SiON film, thepre-coated film may absorb C introduced into the SiOCN film formed onthe wafer 200 when the SiOCN film is formed on the wafer 200, which mayvary in the composition of the film formed on the wafer 200. In order tostabilize the composition of the film formed on the wafer 200, thesecond pre-coated film, which is the outermost surface of the pre-coatedfilm, needs to be formed of a film having the same material as that ofthe film formed on the wafer 200. Furthermore, in this case, it is moredesirable that the second pre-coated film be formed of a film having thesame composition (especially C concentration) as that of the film formedon the wafer 200. This makes it possible to more stabilize thecomposition (especially C concentration) of the film formed on the wafer200.

In addition, it is desirable that the thickness (second thickness) ofthe second pre-coated film (SiOCN film) be set such that the secondpre-coated film is pinhole-free. Specifically, it is desirable that thesecond thickness be set at a thickness of more than 25 Å, for example,at a thickness which falls within a range of more than 25 Å and 150 Å orless, 30 Å or more and 100 Å or less in some embodiments, or 30 Å ormore and 50 Å or less in some embodiments.

Furthermore, the supply order of a Si source, an O source, and a Nsource in the first pre-coating and the supply order of a Si source, a Csource, an O source, and a N source in the second pre-coating be setequal to the supply order of a Si source, a C source, an O source, and aN source in the film formation. This makes it possible to make thecomposition of the pre-coated film formed on the surface in the processcontainer close to the composition of the film formed on the wafer 200,and to more stabilize the C concentration of the SiOCN film formed onthe wafer 200, i.e., the film composition.

After the first pre-coating and the second pre-coating are completed,the interior of the process chamber 201 is purged in the same processingprocedure as that of the purge in the chamber cleaning described above.Thereafter, the internal atmosphere of the process chamber 201 issubstituted by an inert gas.

The pre-coating process is completed by the series of operationsdescribed above. By the pre-coating process described above, it ispossible to suppress the film thickness drop phenomenon from occurringduring the film formation. In addition, by the pre-coating processdescribed above, it is possible to adjust the environments andconditions in the process container before the next film-formingprocess.

(Empty Boat Unloading)

At the pre-coating process is completed, the seal cap 219 is moved downby the boat elevator 115 to open the lower end of the manifold 209.Then, the empty boat 217 is unloaded from the lower end of the manifold209 to the outside of the reaction tube 203 (boat unloading). After theboat unloading, the shutter 219 s is moved so that the lower end openingof the manifold 209 is sealed by the shutter 219 s via the O-ring 220 c(shutter closing).

(3) Effects According to the Present Embodiments

According to the present embodiments, one or more effects as set forthbelow may be achieved.

(a) By forming the SiON film as the first pre-coated film and formingthe SiOCN film as the second pre-coated film thereon in the processcontainer of the substrate processing apparatus (hereinafter, alsoreferred to as the apparatus) which forms the SiOCN film on the wafer toform the pre-coated film in two steps in this way, it is possible toshorten the pre-coating time and to shorten the downtime of theapparatus. That is, it is possible to increase the operating rate of theapparatus and to improve the productivity.

The reason is that the SiOCN film described above is a multi-componentfilm, and therefore, the film-forming time tends to be prolonged. Forexample, in the case of forming a binary film such as a SiN film or thelike, the process per cycle is a two-process of a process of supplying aSi source and a process of supplying a N source, whereas in theformation of a quaternary film such as a SiOCN film or the like, theprocess per cycle is a four-process of a process of supplying a Sisource, a process of supplying a C source, a process of supplying an Osource, and a process of supplying a N source. Therefore, the quaternaryfilm has a longer film-forming time than the binary film by twoprocesses per cycle. In particular, the supply time of the C source (thesupply time of the C₃H₆ gas in the present embodiments) when forming theSiOCN film tends to be longer than the supply time of other processinggases. The supply time of the C source does not greatly affect thesubstantial throughput when the film thickness of the SiOCN film formedon the wafer is relatively small, such as, e.g., 50 to 80 Å. However,even in this case, it may set the film thickness of the pre-coated filmat a thickness which falls within a range of, for example, 200 Å or moreand 400 Å or less or 250 Å or more and 350 Å or less in someembodiments. In this case, the supply time of the C source greatlyaffects the pre-coating time, which causes an increase in the downtimeof the substrate processing apparatus. Furthermore, if the thickness ofthe pre-coated film is set smaller than a thickness which falls withinthe aforementioned range, the film thickness drop phenomenon orparticles may occur. In order to prevent the occurrence of both the filmthickness drop phenomenon and particles, it may form a pre-coated filmhaving a thickness of at least about 200 to 400 Å or about 250 to 350 Åin some embodiments.

In contrast, in the present embodiments, in order to suppress theoccurrence of the film thickness drop phenomenon and particles, apre-coated film having a total thickness of, for example, about 200 to400 Å or about 250 to 350 Å in some embodiments, is formed in theprocess container. Furthermore, at that time, the SiON film is formed asthe first pre-coated film and the SiOCN film is formed as the secondpre-coated film thereon in the process container to form the pre-coatedfilm having a total thickness of about 200 to 400 Å or about 250 to 350Å in some embodiments in two steps in this way. As described above, byforming the pre-coated film in two steps and forming the SiON film whichis a C-free film as the first pre-coated film, the process of supplyingthe C source whose supply time tends to be prolonged may be omitted inthe process of forming the first pre-coated film. Thus, it is possibleto increase the deposition rate and to shorten the pre-coating timeaccordingly.

It may also be considered here that the SiN film is formed as the firstpre-coated film, but the film stress of the SiN film is larger than thefilm stress of the SiON film, and the film stress of the SiON film islarger than the film stress of the SiOCN film. That is, the SiN film hasa larger film stress than that of the SiON film and the SiOCN film, andthus, the film is likely to be cracked and delaminated, leading to thegeneration of particles. Therefore, by using the SiON film having a filmstress smaller than that of the SiN film and close to the film stress ofthe SiOCN film as the first pre-coated film, it is possible to shortenthe pre-coating time while suppressing the generation of cracks in thepre-coated film and the delamination of the pre-coated film.

Furthermore, in the present embodiments, by setting the thickness (firstthickness) of the first pre-coated film which can be formed at arelatively high deposition rate larger than the thickness (secondthickness) of the second pre-coated film which is formed at a relativelylow deposition rate, in other words, by setting the thickness (secondthickness) of the second pre-coated film which is formed at a relativelylow deposition rate smaller than the thickness (first thickness) of thefirst pre-coated film which can be formed at a relatively highdeposition rate, it is possible to further shorten the pre-coating timeand to further shorten the downtime of the apparatus.

(b) By setting the thickness (second thickness) of the second pre-coatedfilm at a thickness of more than 25 Å, which is a thickness at which thesecond pre-coated film is pinhole-free, it is possible to suppress theoccurrence of variation in the C concentration of the SiOCN film formedon the wafer, i.e., the film composition. As a result, it is possible toimprove the quality of the film-forming process.

In this case, if the thickness of the second pre-coated film (SiOCNfilm) is too small, specifically, if the thickness of the secondpre-coated film is 25 Å or less, pinholes may be generated in the secondpre-coated film. When the process of forming the SiOCN film on the waferis performed in the state in which the pinholes are generated in thesecond pre-coated film, the composition of the SiOCN film formed on thewafer may be affected by the first pre-coated film (SiON film) which isan underlayer of the second pre-coated film. Specifically, when formingthe SiOCN film on the wafer, C, which should be originally introducedinto the SiOCN film formed on the wafer, may reach the pre-coated filmthrough the pinholes of the second pre-coated film and may be absorbedby the first pre-coated film. In this case, the C concentration of theSiOCN film formed on the wafer may be lowered.

Furthermore, when the process of forming the SiOCN film on the wafer isrepeated, the SiOCN film is further deposited on the second pre-coatedfilm, and therefore, the effect of pinholes on the second pre-coatedfilm is gradually reduced. However, this means that the degree of Cabsorption by the first pre-coated film may vary every time the processof forming the SiOCN film on the wafer is repeated, which leads to avariation in the C concentration of the SiOCN film formed on the wafer,i.e., the film composition.

This problem can be solved by setting the thickness of the secondpre-coated film at a thickness at which the second pre-coated film ispinhole-free, i.e., by setting the thickness of the second pre-coatedfilm at a thickness of more than 25 Å. Furthermore, by setting thethickness of the second pre-coated film to 30 Å or more, it is possibleto reliably solve the problem.

(c) By setting the thickness (second thickness) of the second pre-coatedfilm to 150 Å or less, it is possible to secure a practical pre-coatingtime shortening effect and to achieve a practical downtime shorteningeffect. If the thickness of the second pre-coated film is too large,specifically, if the thickness of the second pre-coated film is set tomore than 150 Å, the pre-coating time shortening effect may be reduced,and the downtime shortening effect may be reduced. By setting thethickness of the second pre-coated film to 150 Å or less, it is possibleto solve the problem. By setting the thickness of the second pre-coatedfilm to 100 Å or less, it is possible to reliably solve the problem. Bysetting the thickness of the second pre-coated film to 50 Å or less, itis possible to more reliably solve the problem. Moreover, these areparticularly effective when forming the pre-coated film having a totalthickness of, for example, about 200 to 400 Å or about 250 to 350 Å insome embodiments.

(d) By allowing both the first pre-coated film (SiON film) and thesecond pre-coated film (SiOCN film) to contain no elements other thanthe elements contained in the film (SiOCN film) formed on the wafer, itis possible to use the processing gas in the film-forming process ineach pre-coating and it is not required to add the gas supply system forperforming the pre-coating. Thus, it is possible to reduce the cost ofthe apparatus.

(e) By making the supply order of the Si source, the O source, and the Nsource in the first pre-coating and the supply order of the Si source,the C source, the O source, and the N source in the second pre-coatingequal to the supply order of the Si source, the C source, the O source,and the N source in the film formation, it is possible to make thecomposition of the pre-coated film formed in the process container closeto the composition of the film formed on the wafer 200. Thus, it ispossible to more stabilize the C concentration of the SiOCN film formedon the wafer, i.e., the film composition.

(f) By performing the pre-coating process after the cleaning process andperforming the film-forming process after the pre-coating process, it ispossible to adjust the environments and conditions in the processcontainer before the film formation. Furthermore, it is possible tosuppress the generation of particles and the occurrence of filmthickness drop phenomenon in the process container. As a result, itbecomes possible to improve the quality of the film-forming processperformed in the process container. Moreover, it is needless to saythat, by performing the cleaning process and the pre-coating process ina state in which the empty boat is loaded into the process container, itis possible to perform the cleaning process and the pre-coating processeven on the surface of the boat, and to achieve the same effects asthose described above.

(g) The effects of the present embodiments can be similarly achieved inthe case where a precursor gas other than the HCDS gas is used, or inthe case where a C-containing gas other than the C₃H₆ gas is used, or inthe case where an O-containing gas other than the O₂ gas is used, or inthe case where a N- and H-containing gas other than the NH₃ gas is used,or in the case where a cleaning gas other than the F₂ gas is used, or inthe case where an additive gas other than the NO gas is used, or in thecase where an inert gas other than the N₂ gas is used.

Other Embodiments of the Present Disclosure

While one embodiments of the present disclosure has been specificallydescribed above, the present disclosure is not limited to theaforementioned embodiments but may be variously modified withoutdeparting from the spirit of the present disclosure.

In the aforementioned embodiments, the processing sequence ofsequentially performing film formation, chamber cleaning, first nozzlecleaning, second nozzle cleaning, first pre-coating, second pre-coating,and film formation has been illustrated, but any step of chambercleaning, first nozzle cleaning, and second nozzle cleaning may not beperformed, as illustrated in (1) to (6) below. Even in these cases, thesame effects as those of the aforementioned embodiments described withreference to FIGS. 4 and 5 may be achieved.

(1) Film formation→chamber cleaning→first pre-coating→secondpre-coating→film formation

(2) Film formation→first nozzle cleaning→second nozzle cleaning→firstpre-coating→second pre-coating→film formation

(3) First pre-coating→second pre-coating→film formation

(4) Chamber cleaning→first nozzle cleaning→second nozzle cleaning→firstpre-coating→second pre-coating→film formation

(5) Chamber cleaning→first pre-coating→second pre-coating→film formation

(6) First nozzle cleaning→second nozzle cleaning→firstpre-coating→second pre-coating→film formation

Furthermore, in the film formation, films may be formed on the wafer 200by the gas supply sequences illustrated below. Even in these cases, bymaking the supply order of each source in the first pre-coating and thesecond pre-coating equal to that of each source in the film formationand applying the method of the present disclosure, the same effects asthose of the aforementioned embodiments described with reference toFIGS. 4 and 5 may be achieved. The C-containing gas such as the C₃H₆ gasis not limited as being supplied from the gas supply pipe 232 a and thenozzle 249 a but may be supplied from the gas supply pipe 232 b and thenozzle 249 b. Even in this case, the same effects as those of theaforementioned embodiments described with reference to FIGS. 4 and 5 maybe achieved.(HCDS→C₃H₆→NH₃→O₂)×n⇒SiOCN(HCDS→NH₃→C₃H₆→O₂)×n⇒SiOCN(HCDS→NH₃→O₂→C₃H₆)×n⇒SiOCN(C₃H₆→HCDS→C₃H₆→O₂→NH₃)×n⇒SiOCN(C₃H₆→HCDS→C₃H₆→NH₃→O₂)×n⇒SiOCN

Recipes used in each processing may be prepared individually accordingto the processing contents and may be stored in the memory 121 c via atelecommunication line or the external memory 123. Moreover, at thestart of each processing, the CPU 121 a may properly select anappropriate recipe from the recipes stored in the memory 121 c accordingto the processing contents. Thus, it is possible for a single substrateprocessing apparatus to form films of different kinds, compositionratios, film qualities and film thicknesses with enhancedreproducibility. In addition, it is possible to reduce an operator'sburden and to quickly start each processing while avoiding an operationerror.

The recipes mentioned above are not limited to newly-prepared ones butmay be prepared by, for example, modifying the existing recipes alreadyinstalled in the substrate processing apparatus. When modifying therecipes, the modified recipes may be installed in the substrateprocessing apparatus via a telecommunication line or a recording mediumstoring the recipes. In addition, the existing recipes already installedin the substrate processing apparatus may be directly modified byoperating the input/output device 122 of the existing substrateprocessing apparatus.

In the aforementioned embodiments, there has been described an examplein which films are formed using a batch-type substrate processingapparatus capable of processing a plurality of substrates at a time. Thepresent disclosure is not limited to the aforementioned embodiments butmay be appropriately applied to, e.g., a case where films are formedusing a single-wafer-type substrate processing apparatus capable ofprocessing a single substrate or several substrates at a time. Inaddition, in the aforementioned embodiments, there has been described anexample in which films are formed using the substrate processingapparatus provided with a hot-wall-type process furnace. The presentdisclosure is not limited to the aforementioned embodiments but may beappropriately applied to a case where films are formed using a substrateprocessing apparatus provided with a cold-wall-type process furnace.

In the case of using these substrate processing apparatuses, eachprocessing may be performed by the processing procedures and processingconditions similar to those of the aforementioned embodiments. Effectssimilar to those of the aforementioned embodiments may be achieved.

The embodiments described above may be appropriately combined with oneanother. The processing procedures and processing conditions at thistime may be similar to, for example, the processing procedures andprocessing conditions of the aforementioned embodiments.

EXAMPLES

Next, examples will be described.

Example 1

A pre-coated film having a thickness TH₀ (=250 to 350 Å) was formed inthe process container including the inner wall of the reaction tube 203under different pre-coating conditions, and the pre-coating times werecompared.

In a comparative example, as shown in FIG. 6A, a SiOCN film having athickness of TH₀ was formed as a pre-coated film in the processcontainer including the inner wall of the reaction tube 203. In thisexample, as shown in FIG. 6B, a SiON film having a thickness TH₁ (=200to 300 Å) and a SiOCN film having a thickness TH₂ (=30 to 50 Å) wereformed as the pre-coated film in the process container including theinner wall of the reaction tube 203. The processing conditions were setto predetermined conditions which fall within the processing conditionrange in the aforementioned embodiments. FIG. 7 shows a pre-coating timein each of the comparative example and the example.

As shown in FIG. 7, in the comparative example, it took a time of T₀(=600 to 750 minutes) to form the SiOCN film having the thickness TH₀ inthe process container including the inner wall of the reaction tube 203.In contrast, as shown in FIG. 7, in this example, it took a time of T₁(=150 to 200 minutes) to form the SiON film having the thickness TH₁ andit took T₂ (=50 to 100 minutes) to form the SiOCN film having thethickness TH₂ in the process container including the inner wall of thereaction tube 203, i.e., it took a time of T₃ (=200 to 300 minutes) toform the pre-coated film having the thickness TH₀. In other words, inthis example, the pre-coating time could be shortened by T₄ (=400 to 450minutes), i.e., about 60% or more, compared with the comparativeexample.

That is, it could be confirmed that the pre-coated film is formed by twolayers of the SiON film and the thinner SiOCN film by performing thepre-coating in two steps as described above, whereby the pre-coatingtime can be significantly shortened and the downtime of the apparatuscan be significantly reduced, compared with the case where thepre-coated film is formed by the SiOCN film alone.

Example 2

The characteristics of films formed on the wafer by first film formationafter forming the pre-coated film in each process container in which thepre-coated film was formed under different pre-coating conditions inexample 1 were compared.

In a comparative example, a film was formed on the wafer by the firstfilm formation after forming the pre-coated film in the processcontainer in which the pre-coated film was formed by the method of thecomparative example in example 1. In this example, a film was formed onthe wafer by the first film formation after forming the pre-coated filmin the process container in which the pre-coated film was formed by themethod of the example in example 1. The processing procedures andprocessing conditions in the first film formation after forming thepre-coated film were set similar to the comparative example and theexample. FIGS. 8A to 8F show various characteristics of a film formed ineach of the comparative example and the example.

FIG. 8A is a view showing a thickness of a film formed on a waferarranged in each of top (TOP), center (CEN), and bottom (BTM) by thefirst film formation after pre-coating, by comparison between thecomparative example and this example. As shown in FIG. 8A, it wasconfirmed that the thickness of the film formed in this example isequivalent to the thickness of the film formed in the comparativeexample, and the film thickness drop phenomenon does not occur in any ofthem.

FIG. 8B is a view showing a wafer in-plane film thickness uniformity ofthe film formed on the wafer arranged in each of TOP, CEN, and BTM bythe first film formation after pre-coating, by comparison between thecomparative example and this example. As shown in FIG. 8B, it wasconfirmed that the wafer in-wafer film thickness uniformity of the filmformed in this example is equivalent to the wafer in-wafer filmthickness uniformity of the film formed in the comparative example.

FIG. 8C is a view showing a number of particles having a size of 32 nmor more adhered to the film formed on the wafer arranged on each of TOP,CEN, and BTM by the first film formation after pre-coating, bycomparison between the comparative example and this example. As shown inFIG. 8C, it was confirmed that the number of particles adhered to thefilm formed in this example is smaller than the number of particlesadhered to the film formed in the comparative example, which isexcellent in each region.

FIG. 8D is a view showing a refractive index of the film formed on thewafer arranged in each of TOP, CEN, and BTM by the first film formationafter pre-coating, by comparison between the comparative example andthis example. As shown in FIG. 8D, it was confirmed that the refractiveindex of the film formed in this example is equivalent to the refractiveindex of the film formed in the comparative example.

FIG. 8E is a view showing a composition ratio of the film formed on thewafer by the first film formation after pre-coating, by comparisonbetween the comparative example and this example. That is, FIG. 8E is aview showing an atomic concentration of Si, O, C, and N, i.e., acomposition ratio, of the film formed in each of the comparative exampleand this example. As shown in FIG. 8E, it was confirmed that thecomposition ratio of the film formed in this example is equivalent tothe composition ratio of the film formed in the comparative example.

FIG. 8F shows a wet etching rate when the film formed on the wafer bythe first film formation after pre-coating is immersed in a 1% HFaqueous solution, by comparison between the comparative example and thepresent example. As shown in FIG. 8F, it was confirmed that the wetetching rate of the film formed in this example is equivalent to the wetetching rate of the film formed in the comparative example.

That is, it was confirmed that, even when the film was formed on thewafer by the method of this example, it is possible to obtain the filmhaving the same quality as when the film was formed on the wafer by themethod of the comparative example.

According to the present disclosure in some embodiments, it is possibleto improve a productivity by shortening a downtime of a substrateprocessing apparatus.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the disclosures. Indeed, the embodiments described herein maybe embodied in a variety of other forms. Furthermore, various omissions,substitutions and changes in the form of the embodiments describedherein may be made without departing from the spirit of the disclosures.The accompanying claims and their equivalents are intended to cover suchforms or modifications as would fall within the scope and spirit of thedisclosures.

What is claimed is:
 1. A method of manufacturing a semiconductor device,comprising: (a) forming a film on a substrate by supplying a firstprocessing gas to the substrate in a process container; (b) forming afirst pre-coated film, which is an oxynitride film having a firstthickness and having a material different from a material of the filmformed in (a), in the process container by supplying a second processinggas into the process container in a state in which the substrate doesnot exist in the process container; and (c) forming a second pre-coatedfilm, which is an oxycarbonitride film having a second thickness smallerthan the first thickness and having the same material as the material ofthe film formed in (a), on the first pre-coated film formed in theprocess container by supplying a third processing gas into the processcontainer in the state in which the substrate does not exist in theprocess container.
 2. The method according to claim 1, wherein both thefirst pre-coated film and the second pre-coated film contain no elementother than elements contained in the film formed in (a).
 3. The methodaccording to claim 1, wherein the first pre-coated film is a carbon-freefilm, and the second pre-coated film is a carbon-containing film.
 4. Themethod according to claim 1, wherein the film formed in (a) containssilicon, oxygen, carbon, and nitrogen, the first pre-coated filmcontains silicon, oxygen, and nitrogen, and the second pre-coated filmcontains silicon, oxygen, carbon, and nitrogen.
 5. The method accordingto claim 1, wherein the film formed in (a) is a silicon oxycarbonitridefilm, the first pre-coated film is a silicon oxynitride film, and thesecond pre-coated film is a silicon oxycarbonitride film.
 6. The methodaccording to claim 1, wherein in (b), the first pre-coated film isformed by performing a cycle a predetermined number of times, the cycleincluding non-simultaneously supplying a silicon-containing gas, anoxygen-containing gas, and a nitrogen-containing gas as the secondprocessing gas into the process container, and wherein in (c), thesecond pre-coated film is formed by performing a cycle a predeterminednumber of times, the cycle including non-simultaneously supplying asilicon-containing gas, a carbon-containing gas, an oxygen-containinggas, and a nitrogen-containing gas as the third processing gas into theprocess container.
 7. The method according to claim 6, wherein in (a),the film formed in (a) is formed by performing a cycle a predeterminednumber of times, the cycle including non-simultaneously supplying asilicon-containing gas, a carbon-containing gas, an oxygen-containinggas, and a nitrogen-containing gas as the first processing gas to thesubstrate in the process container, and wherein a supply order of thesilicon-containing gas, the oxygen-containing gas, and thenitrogen-containing gas in (b) and a supply order of thesilicon-containing gas, the carbon-containing gas, the oxygen-containinggas, and the nitrogen-containing gas in (c) are set equal to a supplyorder of the silicon-containing gas, the carbon-containing gas, theoxygen-containing gas, and the nitrogen-containing gas in (a).
 8. Themethod according to claim 7, wherein in (a), the silicon-containing gas,the carbon-containing gas, the oxygen-containing gas, and thenitrogen-containing gas are sequentially supplied in this order, whereinin (b), the silicon-containing gas, the oxygen-containing gas, and thenitrogen-containing gas are sequentially supplied in this order, andwherein in (c), the silicon-containing gas, the carbon-containing gas,the oxygen-containing gas, and the nitrogen-containing gas aresequentially supplied in this order.
 9. The method according to claim 1,wherein the second thickness is a thickness at which the secondpre-coated film is pinhole-free.
 10. The method according to claim 1,wherein the second thickness is more than 25 Å and 150 Å or less. 11.The method according to claim 1, wherein the second thickness is 30 Å ormore and 100 Å or less.
 12. The method according to claim 1, wherein thesecond thickness is 30 Å or more and 50 Å or less.
 13. The methodaccording to claim 1, wherein after (b) and (c) are performed, (a) isperformed.
 14. The method according to claim 1, further comprising: (d)removing deposits deposited in the process container by supplying acleaning gas into the process container in the state in which thesubstrate does not exist in the process container, before performing (b)and (c).
 15. The method according to claim 14, wherein (d), (b), and (c)are sequentially performed in this order, and then, (a) is performed.16. The method according to claim 14, wherein after (a) is performed,(d), (b), and (c) are sequentially performed in this order.
 17. Themethod according to claim 14, wherein after (a) is performed, (d), (b),and (c) are sequentially performed in this order, and then, (a) isperformed.
 18. A substrate processing apparatus, comprising: a processcontainer in which a substrate is processed; a first processing gassupply system configured to supply a first processing gas into theprocess container; a second processing gas supply system configured tosupply a second processing gas into the process container; a thirdprocessing gas supply system configured to supply a third processing gasinto the process container; and a controller configured to be capable ofcontrolling the first processing gas supply system, the secondprocessing gas supply system, and the third processing gas supply systemso as to perform a process, the process comprising: (a) forming a filmon the substrate by supplying the first processing gas to the substratein the process container; (b) forming a first pre-coated film, which isan oxynitride film having a first thickness and having a materialdifferent from a material of the film formed in (a), in the processcontainer by supplying the second processing gas into the processcontainer in a state in which the substrate does not exist in theprocess container; and (c) forming a second pre-coated film, which is anoxycarbonitride film having a second thickness smaller than the firstthickness and having the same material as the material of the filmformed in (a), on the first pre-coated film formed in the processcontainer by supplying the third processing gas into the processcontainer in the state in which the substrate does not exist in theprocess container.
 19. A non-transitory computer-readable recordingmedium storing a program that causes, by a computer, a substrateprocessing apparatus to perform a process, the process comprising: (a)forming a film on a substrate by supplying a first processing gas to thesubstrate in a process container of the substrate processing apparatus;(b) forming a first pre-coated film, which is an oxynitride film filmhaving a first thickness and having a material different from a materialof the film formed in (a), in the process container by supplying asecond processing gas into the process container in a state in which thesubstrate does not exist in the process container; and (c) forming asecond pre-coated film, which is an oxycarbonitride film having a secondthickness smaller than the first thickness and having the same materialas the material of the film formed in (a), on the first pre-coated filmformed in the process container by supplying a third processing gas intothe process container in the state in which the substrate does not existin the process container.
 20. A method of processing a substrate,comprising: (a) forming a film on the substrate by supplying a firstprocessing gas to the substrate in a process container; (b) forming afirst pre-coated film, which is an oxynitride film having a firstthickness and having a material different from a material of the filmformed in (a), in the process container by supplying a second processinggas into the process container in a state in which the substrate doesnot exist in the process container; and (c) forming a second pre-coatedfilm, which is an oxycarbonitride film having a second thickness smallerthan the first thickness and having the same material as the material ofthe film formed in (a), on the first pre-coated film formed in theprocess container by supplying a third processing gas into the processcontainer in the state in which the substrate does not exist in theprocess container.